THE IMPACT OF SYNTHETIC ORGANIC
COMPOUNDS ON ESTUARINE ECOSYSTEMS
box 15587 • sarasota, fla. 33579 ¦ (813) 959-593/
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THE IMPACT OF SYNTHETIC ORGANIC
COMPOUNDS ON ESTUARINE ECOSYSTEMS
to
Thomas Duke, Ph.D.
Environmental Protection Agency
Gulf Breeze, Florida 32561
by
Jeffrey L. Lincer, Ph.D.
Eco-Analysts, Inc.
Post Office Box 15587
Sarasota, Florida 33579
FINAL REPORT
Submitted: 1 November 1974
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TABLE OF CONTENTS
Subject Page
Title Page . . . . . 1
Table of Contents . . it
I. INTRODUCTION 1
II. PRESENCE OF SYNTHETIC ORGANICS IN ESTUARIES ... 8
Pesticides 8
Industrial Toxicants ....... 10
.III. BIOLOGICAL EFFECTS OF SYNTHETIC ORGANICS ON
ESTUARINE LIFE . 12
Pesticides .......... 12
Industrial Toxicants 16
-Synergism and Modifying Effects ....... . . 18
The Effect(s) of Synthetic Organics at the
Estuarine Ecosystem Level . . ..... . . . . 19
IV. RECOMMENDED RESEARCH 20
-APPENDIX A 23
APPENDIX B . . ... 29
APPENDIX C 37
LITERATURE CITED 39
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I. INTRODUCTION
For the purposes considered herein, the term "synthetic
organic compounds" refers to man-made compounds and includes
pesticides, polychlorinated biphenyls (PCB's), hexachloro-
benzene (HCB) and phthalate esters (PAE's) as well as toxic
contaminants of some of these, like chlorinated dibenzodioxins
and dibenzofurans.
The "estuarine ecosystem" has been variously defined but
for the sake of simplicity it will be considered as that zone
of interface where fresh- and salt water mix. This estuarine
ecosystem serves a vital function in that most marine finfish
and shellfish depend on a high quality estuary for some critical
portion of their life history (Clark, et al_., 1969; Douglas and
Stroud, 1971). In addition, many salmonids and other anadromous
fishes spend a variable amount of time in this habitat before
ascending the rivers to spawn.
Unfortunately, the oceans are the recipients and ultimate
accumulation sites for persistent pollutants like organochlorines
(Dustman and Stickel, 1966; Risebrough, et_ al_., 1972). In fact,
an estimated 25 percent of all DDT applied to the land has found
Its way to the sea (S.C.E.P., 1970). Risebrough and his co-
workers (1968a) indicate that 11 tons of DDT per year is trans-
ported down the Mississippi River to the Gulf of Mexico alone!
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Because of their unique physical and chemical characteristics,
estuaries tend to be "toxicant traps". The detritus which forms
the base of the estuarine food chain may contain up to 50 ppm
total DDT (Odum, et^ al_., 1969) and Woodwell, et^ al_. (1967) es-
timated that total estuarine ecosystem levels as high as 14.7
kg/hectare were possible.
DDT and other synthetic organics are termed "toxic" when,
because of their physical or chemical properties, they interfere
with normal biological functions. The interference can occur at
any level; whether it be as subtle as pesticide-induced decreased
growth in oysters or as gross as reproductive failure in bald
eagles or mass fish mortality. There are naturally-occurring
toxic substances which include such things as the resin from
certain plants and the toxin(s) associated with red tide organisms.
By far, however, most deleterious substances find their origin with
modern-day man and his efforts to promote "progress".
A logical breakdown of synthetic organic compounds which
are considered in this paper along with available production and/or
consumption information follows:
1. Pesticides are chemicals which kill organisms identified
as "pests" and include insecticides, fungicides, piscicides,
herbicides, miticides, etc. Insecticides are commonly broken
down into: (a) chlorinated hydrocarbons (organochlorines), like
DDT, aldrin, dieldrin, heptachlor, toxaphene and chlordane; (b)
organophosphates, like malathion, parathion, diazinon and guthion;
and (c) carbamates, like Sevin and zectran. Fungicides include
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such things as dithiocarbamates (e.g., ferbam and ziram), nitrogen-
containing compounds (e.g., phenylmercuric acetate), triazines,
qui nones, heterocyclics and inorganics like the heavy metals.
Hexachlorobenzene (CgClg or HCB) is a fungicide but is, in addi-
tion, used in organic synthesis processes. Herbicides are quite
varied with the most common being the phenoxy acids like 2,4-D
and 2,4,5-T. Frequently-used aquatic herbicides include endothal
and diquat which are often used in combination with a surfactant
(like a detergent).
The U. S. production of the major synthetic organic pesticides
is reproduced in Table 1. In 1971, the production of synthetic
organic insecticides in the United States climbed nearly 14 per
cent from the year before, reaching 557.7 million pounds, third
highest on record (Fowler, 1973). Insecticides accounted for 49
per cent of the tonnage of synthetic pesticides produced. As you
can see in Table 1, the trend was reversed for 1972.
Table 2 reveals the domestic disappearance of selected pesti-
cides for the years 1966 through 1971. Except for the aldrin-
toxaphene group, there is a fairly consistent downward trend.
Domestic disappearance of DDT, for instance, was 18.2 million pounds
in 1971 which was down more than 28 per cent from 1970. The con-
sumption of the aldrin-toxaphene group continued its rise during
1972. Sales for that group (not including Strobane®) soared
to 140 million pounds for 1972 (U. S. Tariff Commission, 1974).
2. "Industrial Toxicants" is a catch-all term that has been
variously subdivided. Polychlorinated biphenyls (PCB's) are
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Table 1. U. S. production of synthetic organic pesticides by class, 1967-1972; In thousands of pounds.
1967* 1968* 1969* 1970* 1971* 1972**
Fungicides 177,886 190,773 182,091 168,470 180,270 142,812
Herbicides 439,965 499,514 423,840 434,241 458,849 451,311
Insecticides,
fumigants, 503,796 581,619 580,884 495,432 564,818 563,575
rodenticides*
Total 1 ,029,956 1 ,175,173 1 ,134,739 1 ,054,567 1 ,203,937 1,157,698
* Fowler, 1973
** United States Tariff Commission, 1974.
t Includes small quantity of synthetic soil conditioners; does not include the fumigants carbon tetrachloride,
paradichlorobenzene or inorganic rodentlcides.
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Table 2. Domestic disappearance of selected pesticides at producers'
level, United States, 1966 - 1971. In thousands of pounds. (Fowler,
1973).
Pesticide
1966*
1967*
1968*
1969*
1970t
19711
Aldrinrtoxaphene
group
86,646
86,289
38,710
89,721
62,282
85,005
Calcium arsenate
2,942
2,329
1,992
2,117
2,900
2,457
Copper sulfate
104,020
85,274
87,452
99,840
77,344
70,272
DDT
45,603
40,257
32,753
30,256
25,457
18,234
Lead arsenate
6,944
6,152
4,747
7,721
5,860
4,142
2,4-D
63,903
66,955
68,404
49,526
46,942
32,174
2,4,5-T
17,080
15,381
15,804
3,218
4,871
1,389
* Year ending September 30.
t Year ending December 31.
** Includes aldrin, chlordane, dieldrin, endrin, heptachlor, Strobane
and toxaphene.
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chlorinated compounds which find use in almost every sector of
modern man's world and have recently come under close scrutiny
(Peakall and Lincer, 1970). In the past, they have been used in
such diverse products as printer's ink to swimming pool paint,
however, a voluntary curtailment by Monsanto has restricted their
use.
Phthalate esters (PAE's) were introduced in the 1920's to
overcome the problems of camphor in the plasticizer industry.
Major uses of PAE's include construction products, automobile and
home furnishings, clothing, food coverings and medical products.
Phthalates are also found in biochemical pathways and several
natural products such as poppies and tobacco leaves (Graham,1973;
Mathur, 1974). The documentation that PAE's were readily extracted
into blood from plastic storage bags and other medical devices was
the original basis for the fear that the human population might
be continuously exposed (Anonymous, 1973).
PCB's and PCT's (polychlorinated terphenyls) are produced under
the tradename Aroclor®by Monsanto in the United States. PCB
production peaked during the period 1967 - 1970 (Table 3). PCT
production shows a similar, but later, production peak during 1970 -
1971. PCT's are no longer being produced and the manufacture of
PCB's is directed exclusively towards the heat transfer, trans-
former and capacitor sales categories. In an effort to overcome
some of the potential environmental problems of exisiting biphenyls,
Aroclor 1016 was produced. Approximately 23.5 million pounds of
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Table 3. Production of polychlorinated biphenyls (PCB's) and
polychlorinated terphenyls (PCT's) by Monsanto Industrial Chemicals
Company for years 1959 - 1973. (Pers. comm., W. B. Papageorge).
U. S. PRODUCTION (THOUSANDS OF POUNDS)
Year PCB's PCT's
1959
*
2,996
1960
37,919
3,850
1961
36,515
2,322
1962
38,353
4,468
1963
44,734
4,920
1964
50,833
5,288
1 965
60,480
6,470
1966
65,849
8,190
1967
75,309
9,450
1 968
82,854
8,870
1969
76,389
11,600
1970
85,054
17,768
1971
34,994
20,212
1972
38,600
8,134
1973
42,178
**
* Data unavailable.
** Production terminated in April, 1972.
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Aroclor 1016 were sold domestically in 1973. The 1973 sales for
Aroclors 1221, 1242 and 1254 were recorded at 0.04, 6.20 and 9.98
million pounds, respectively. All other PCB's showed no domestic
sales (pers. comm., W. B. Papageorge).
"Plasticizers" are obviously produced by a variety of manufac-
turers, however, phthalates (DOP, DIOP, DIDP and linear) are the
major groups consumed (Table 4). During 1972, production of phthalic
anhydride esters totaled 1,145,693 pounds and sales followed closely
at 1,138,493 pounds (U. S. Tariff Commission, 1974).
II. PRESENCE OF SYNTHETIC ORGANICS IN ESTUARIES
Pesticides. Considering only the organochlorine pesticides, DDE
(the major breakdown product of DDT) is probably the most widely
distributed in fish and wildlife (see Appendix A). Being lipophilic
(i.e., "fat-loving"), DDE like other organochlorines is not very
soluble in water but accumulates in the fat of organisms (for over-
view, see Table 1 in reference entitled E.P.A.,no date). Organochlorine
pesticides are passed from prey to predator with little lost by
way of excretion. This "biological magnification" with each transfer
from one food level (i.e., trophic level) to the next results in
animals at the tops of food chains acquiring inordinate amounts of
these poisons (Woodwell, et^ al_., 1967). For instance, DDE concentra-
tion reached 1,100 ppm (parts per million) in the fat of brown pelican
.eggs collected off the coast of California and 1,000 ppm in the eggs
of the white-tailed eagle collected in the Baltic (Risebrough, et al.,
1972).
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Table 4. Consumption of plasticizers by type (in thousand metric
tons)*.
Plasticizer
1972
1973
1974
Adipates
28.0
28.4
27.3
Azelates
6.8
7.2
7.3
DOP/DIOP/DIDP
345.0
379.5
363.6
Epoxy
50.0
56.8
59.1
Linear phthalates
109.0
125.5
143.2
Polyesters
22.7
25.4
24.1
Trimellitates
8.1
8.5
10.5
Others
110.0
113.0
113.6
Total
679.6
744.3
748.7
*Source: Anonymous, initialed R.M. (1974).
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Organochlorine pesticides are readily accumulated by shellfish
and this characteristic has been taken advantage of to characterize
the geographic distribution of pesticide contamination. As part
of the National Pesticide Monitoring Program by E.P.A. (Butler, 1973),
shellfish were collected from coastal zones of the United States.
Analyses of over 8,000 samples for 15 persistent organochlorines showed
that DDT-type residues were ubiquitous, with the maximum DDT level at
approximately 5 ppm. Dieldrin was the second most-commonly detected
compound with a maximum of 0.23 ppm. Other organochlorine pesticides
found occasionally which are also extremely toxic to estuarine life,
included endrin, mirex and toxaphene.
Although most organophosphate and carbamate pesticides are ad-
vertized as short-lived, there is evidence that some may not be. In
an application of carbaryl (Sevin) at rates comparable to those used
to control oyster pests, the chemical could still be detected in the
mud 42 days post-treatment (Karinen, et^al_., 1967). Similarly, 14
days after a standard ground application of malathion, the organo-
phosphate could still be found in the estuarine plant Juncus (Tagatz,
et al_., 1974).
The fungicide hexachlorobenzene (HCB), has recently been reported
in several species of freshwater and some species of anadromous fishes
including coho salmon from Michigan and stiped bass from Maryland and
•Florida (Johnson, et_al_., 1974).
Industrial Toxicants. Polychlorinated biphenyls (PCB's) are as^
widely distributed as DDT. Because of similar molecular shape and
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composition, the physical and chemical properties of PCB's also
confer the same lipophilic characteristic that allows biological
accumulation and food chain magnification.
Estuarine organisms like fiddler crabs and shrimp readily pick
up PCB's from the sediments (Nimmo, et^ al_., 1971a) and filter-feeding
oysters accumulate these chemicals, like organochlorine pesticides,
from the water (Lowe, et^ al_., 1972).
Like the organochlorine pesticides, PCB's accumulate to high
levels in organisms representing the tops of food chains. Fat from
the eggs of California brown pelicans contained 200 ppm PCB's while
similar samples from the Baltic white-tailed eagle contained 540 ppm
(Risebrough, et_ al_., 1972).
There is an ever-increasing list of "industrial toxicants" that
have been found in our waterways. Phthalate esters have been found
in water collected from the Charles River in New England. Levels
of 0.88 - 1.9 ppb were reported with higher levels associated with
increasing distances upstream (Hites, 1973). Mayer, et^ al_. (1972)
reported on PAE's in selected samples from North America. They
found from 0.09 ppb DNBP (di-n-butyl phthalate) in Missouri River
water to 200 ppb in Mississippi River channel catfish and 500 ppb
in tadpoles. Similar values for another phthalate, DEHP (di-2-
ethylhexyl phthalate), were 4.9, 400 and 300 ppb. These residue
levels were roughly comparable to PCB levels in the same samples.
Although the above rivers drain directly into estuaries and
one suspects that phthalates, like other adsorbed toxicants, would
"salt out" upon reaching the saline environment, apparently no
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published research on phthalates has been directed towards that
habitat.
Although the preliminary work of Bowes, et al., (1973), was
directed at determining levels of chlorinated dibenzofurans and
dibenzodioxins in wildlife populations exhibiting embryonic mor-
tality, it did not reveal either of these two compounds. However,
they reported hexachloronaphthalene in gull eggs but no chlorinated
compounds of interest in sea lion samples.
III. BIOLOGICAL EFFECTS OF SYNTHETIC ORGANICS ON ESTUARINE LIFE
Pesticides. Organochlorine insecticides have been shown to
interfere with almost every level of biological function tested in
marine life (see Appendix B). Levels of DDT in the water as low
as 0.001 ppm caused marked reduction in oyster growth (Butler, 1966a)
and high levels of organochlorines have been associated with terato-
genic effects in terns (Hays and Risebrough, 1972) and premature
births in marine mammals (DeLong, et ah, 1973).
Some organochlorines, like Mirex, a chemical used to control
the imported fire ant, Solenopsis saevissima in the southeastern
states, are particularly toxic to estuarine organisms. For example,
juvenile shrimp and crabs died when exposed to one particle of mirex
bait; and 1 ppb (part per billion) mirex in sea water killed 100
per cent of the shrimp exposed (Lowe, et al., 1971a).Similarly,
0.1 ppm dietary dieldrin brought about maladaptive behavior in
fiddler crabs (Klein and Lincer, 1973).
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Some urea herbicides, like Diuron, significantly inhibit the
growth of marine algae at levels as low as 1 ppb (Walsh and Grow,
1971) and a few parts per million of DDT, dieldrin or endrin is
enough to reduce phytoplankton photosynthesis (Wurster, 1968; Menzel,
et al., 1970).
Hexachlorobenzene has been shown to be especially toxic to birds
under laboratory conditions (Vos, ert al_., 1968), but no tests on
estuarine species have been reported to the author's knowledge.
The sensitivity of a particular taxonomic group to any particular
toxicant will vary appreciably. Although toxic to crustaceans, the
carbamate Sevin is fairly nontoxic to fish and mammals (Lowe, 1967).
In very general terms, Table 5 (reworked from Butler, 1966b)displays
the relative toxicities of different pesticide groups to estuarine
fauna.
In a toxicity test which included 12 insecticides and seven
species of estuarine fish, the descending order of toxicity was:
endrin, DDT, dieldrin, aldrin, dioxathion, heptachlor, lindane,
methoxychlor, Phosdrin, malathion, DDVP, and methyl parathion
(Eisler, 1970). For a more comprehensive listing of the toxic ef-
fects on estuarine life, by pesticide, the reader is encouraged to
read App. Table 3 of E.P.A., no date.
California seems to have taken the lead in 1963 in describing
the presence and effects of pesticides relative to water quality
criteria (McKee and Wolf, 1963). This precipitated many studies
and many questions. Perhaps the most important question a decision-
making politician or coastal-zone administrator ought to ask with
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Table 5. Relative sensitivity of typical estuarine organisms to
three major groups of pesticides. Higher numbers reflect greater
sensitivity. Reworked from Butler, 1966b.
Pesticide Type
Organism
Herbicides
Organophosphates
Organochlorines
Plankton
1
0.5
3
Shrimp
1
1,000
300
Crab
1
800
100
Oyster
1
1
100
Fish
1
2
500
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reference to toxic discharges is "How much should be allowed in our
waters and what chemicals should not be applied at all near the
estuaries?" Attempts have been made to answer these and similar
questions. The National Technical Advisory Committee to the Secretary
of the Interior (1968) zoned in on this topic and recommended that
the following organochlorines not be applied near the marine habitat
because of their extreme toxicity:
Aldrin DDT
BHC Dieldrin
Chlordane Endosulfan
Endrin Methoxychlor
Heptachlor Perthane
Lindane TDE
Toxaphene
Mirex has been shown to be exceptionally toxic to estuarine in-
vertebrates like shrimp and should be considered in this category.
Hexachlorobenzene is particularly toxic to birds (Vos, et al_., 1968)
and deserves special attention around rookeries.
A similar list for organophosphates included:
Coumophos Naled
Dursban Parathion
Fenthion Ronnel
The above organochlorines and organophosphates are acutely toxic
at concentrations of 5 mg/1 or less and should not be permitted to
exceed 50 nanograms/1. The next group they discussed is generally
not quite as toxic but should not be allowed to exceed 10 mg/1 in
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estuarine waters. This group included:
Arsenicals
2,4,5-T compounds
Phthalic acid compounds
Botanicals
2,4-D compounds
Carbamates
Triazine compounds
Substituted urea compounds
This kind of information and guidance as to allowable levels of
these and most other common toxicants, including radionuclides, heavy
metals, PCB's, etc. is presently being updated by the Environmental
Protection Agency (see National Academy of Science and National Academy
of Engineering, 1972).
Industrial Toxicants. A great deal of research has been carried
out on the effects of PCB's on estuarine life (Appendix B). Perhaps
most of it has been done at the E.P.A. Gulf Breeze Laboratory. PCB's
have been shown to significantly decrease oyster growth at levels as
low as 5 ppb (Lowe, et al_., 1972) and be lethal to shrimp at 1 ppb
(Nimmo, et^ al_., 1971b). Duke, et a1_. (1970) showed that crabs concen-
trated the PCB Aroclor 1254 and 72 per cent of the shrimp exposed to
5 ppb died after day 10. Hansen, et al_. (1974a) demonstrated that
estuarine fishes and shrimp displayed varying degrees of avoidance
to the same PCB at levels 0.001 to 10 ppm. Bioassays with Aroclor
1254 indicated that 5 ppb caused mortality to estuarine fish and
the effect was delayed (Hansen, et^ al_., 1971). In response to the
change in emphasis of PCB production and subsequent increase in
Aroclor 1016 manufacture, Hansen and co-workers (1974b) established
the acute 96-hour LC^q's for estuarine shrimp, fish and oyster.
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The biochemical effects of PCB's have also come under scrutiny.
Keil, et_ah (1971) tested the effects of Aroclor 1242 (0.01-0.1 ppm)
on marine diatoms and found that it inhibited growth, RNA synthesis
and chlorophyll production. Aroclor 1221 has been shown capable of
impairing osmoregulation in the killifish at relatively high levels
(7.5-75 ppm) by Kinter, et al. ,(1972).
Although no work has apparently been done on the effects of PCB's
on estuarine fish-eating birds, some data are available on ducks.
Friend and Trainer (1970) showed a marked influence of Aroclor 1254
on the duck's susceptability to viral infection. Heath, et al_. (1972),
testing a series of PCB's, revealed that toxicity was positively cor-
related with degree of chlorination and Haegele and Tucker (1974)
established the effect of 1254 on eggshell thinning.
Very little toxicological work has been done with dioxins, di-
benzofurans and phthalates and nothing has been directed at the estuarine
habitat to the author's knowledge. Miller, et^al_. (1973) reported on
the effects of tetrachloro-dibenzo-dioxin (TCDD) on various aquatic
organisms. Approximately 50 per cent of the young coho salmon exposed
to 131 ng/1 died by day 20. They also showed a marked growth inhibition
by TCDD on both salmon and rainbow trout.
Zitko and his colleagues (1973) reported on the acute and chronic
oral toxicity of chlorinated dibenzofurans to immature brook trout.
They concluded that 2,8-dichlorodibenzofuran has a low acute toxicity
\
to that species since even a high level of 122 mg/kg produced no
mortality.
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Work on phthalate esters has been limited to freshwater or
anadromous organisms. In an effort to establish LC50 values for
freshwater organisms, Mayer and Sanders (1973) reported DNBP to be
less toxic to rainbow trout (96-hour LC50 = 6.5 mg/1) than to the
other fish tested. Phthalate esters are metabolized by freshwater
fishes (Stalling, et^ al_., 1973) and both DEHP and DNBP are apparently
not especially (acutely) toxic to freshwater invertebrates. Sanders,
et al_. (1973) reported that although invertebrates rapidly accumulate
these compounds, their 96-hour TL^q (2.1 -.>32 mg/1) is appreciably
greater than DDT, by comparison. However, the TL^q values for aquatic
organisms are 700 to 11,000 times that which inhibited reproduction
in one of the invertebrates tested (waterfleas).
Synergism and Modifying Effects. No report, however brief, on
the effects of synthetic organics on estuarine life would be complete
without including the area of synergistic effects and modifying factors.
The term "synergism", unfortunately, has many definitions. For our
present needs, we will consider it to mean more than the anticipated
additive effects.
This subject has been addressed in depth elsewhere (Livingston,
et al_., in press) however, a few examples of this phenomenon which are
particularly germane to the estuary will follow. Once again, most
•t
work in this area has been done in freshwater, however, Lowe, et al.
(1971b) reported that oysters exposed toa mixture of 1 mg/1 each of
DDT, toxaphene and parathion showed reduced growth and histopathological
effects. When these mollusks were exposed to the individual pesticides,
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similar results were not observed.
Eisler (1970) reported on the modifying factors affecting the
toxicity of organochlorines and organophosphates to the muirimichog,
an estuarine fish. The toxicity of organophosphates increased with
increasing temperature and salinity and decreasing pH. The toxicity
of organochlorines was greatest at intermediate temperatures (20 -
25 C) and least at an intermediate pH (7 - 8). Salinity had little
effect on organochlorine toxicity.
Nimmo (1973) reported that sublethal levels of the PCB, Aroclor
1254, became lethal to estuarine penaeid shrimp when the test organisms
were stressed by reduced salinity. Since this species is migratory
and experiences a wide variation in salinity, this finding is particu-
larly significant.
The effect of temperature may be of paramount importance in
modifying the toxicity of pesticides to estuarine invertebrates. For
example, Koenig, et al_. (in prep.) found that blue crabs contaminated
with DDT did not die in a field experiment until a cold front caused
significant reductions in water temperature.
The Effect(s) of Synthetic Organics at the Estuarine Ecosystem
Level. With all due deference to the title of this report, pitifully
little research has been addressed to the "ecosystem" level.
Although a variable amount of effort has gone into testing the
effects of particular toxicants under "field conditions" (see Appendix
C), this is still not approaching the problem on the ecosystem level.
Odum and others have developed methods for simulating ecosystem
energy and material flow on analog computers, but this approach is
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still twice-removed from reality. On the other hand, such models
often indicate what types of information are lacking and also have
the advantage that the effects of even extreme manipulations can be
tested through many generations or seasonal cycles without any damage
to the real world.
Even at the community level, little has been done with respect
to the effects of synthetic organics. A variety of community parameters
have been suggested as reflectors of a community's health. Margalef's
"species richness" and Peilou's "species diversity and eveness" are
but a few. Researchers are only now finding out'that many of these
parameters are not the panaceas they thought they were. The main
problem lies with trying to use these techniques out of the context
for which they were originally intended.
If it is possible to consistently and accurately describe some
ecosystem parameter, then it ought to be theoretically possible to
quantitate a change in that parameter. The absence of this kind of
effort in the estuarine and other habitats is merely a reflection of
our current inability to describe such changes, not evidence of its
non-existence.
IV. RECOMMENDED RESEARCH
As an overview, emphasis in future research should be given to
determining the significance of the residues being reported in the
literature. This can be accomplished by stressing the diagnostic
aspects of experimentation during the planning stage and encouraging
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toxicological studies that have direct relevance to the real world.
In this light, the area of field-testing toxicants has progressed
in a manner that reflects individual idiosyncrasies and the idiomatic
characteristic(s) of the funding and/or research organization (Appendix
C). Efforts should be made to , at least, roughly standardize field
testing techniques with a keen awareness of the possible modifying
and synergistic effects that one will encounter in the estuary.
Interpretation of field exposures will require coordinated efforts
in the laboratory under less real, but more controlled, conditions.
It is only there that statistically and logistically complicated
designs can reach fruition and elucidate specific modes of action,
synergy, latent effects, food-chain magnification, etc.
On the global scene, interdisciplinary efforts should be made
to more thoroughly characterize the kinetics, marketing patterns and
use of widespread synthetic organic compounds, like phthalate esters,
other plasticizers, chlorinated dibenzofurans and dioxins and HCB.
We need to know more about their environmental kinetics, especially
their metabolism in soil and water.
As to specific chemicals that need experimental attention, PAE's,
HCB, dioxins and dibenzofurans are high on the list.
PAE's are widespread in freshwater fish with higher residues
appearing to be associated with industrial areas (Stalling, et al.,
1973). They have been shown to be more toxic to aquatic organisms
than warm-blooded animals. These esters disturb reproduction and
growth in aquatic invertebrates and fish yet nothing is known about
-------
22
their effects on estuarine species.
Although not widely reported in the literature, HCB has been
found in environmental samples (Holden, 1970). In view of the possible
analytical confusion with benzene hexachloride (BHC), HBC may be even
more widespread. With this potential and the documented toxicity of
this compound to birds in mind (Vos, et^ al_., 1968), the effects of
HCB on fish-eating birds is of concern.
The initial work with the dioxin TCDD indicates important effects
on the growth and reproduction of anadromous and freshwater species
(Miller, et al_., 1973). Again, nothing is known about the effects on
estuarine species.
Dibenzofurans were not particularly lethal to the trout they were
tested on (Zitko, et^ al_., 1973), however, nothing is known about their
sublethal effects. In addition, because of different osmoregulatory
mechanisms, the effect(s) on euryhaline species may be considerably
different.
As to the level of emphasis and the parameters that need attention,
efforts should be made to characterize effects at the ecosystem and/or
community level. This is the final biological-physical-chemical integra-
tion that will reflect individual perturbations at any sublevel if,
in fact, they are significant. As a prelude to this, more intensive
research is necessary on the sublethal effects, with special emphasis
on behavior and biochemistry. In terms of the experimental design of
laboratory studies, more attention should be given to synergistic
effects and latent responses. With reference to the former, research
aimed at elucidating the modifying effects of sewerage and storm run-
off is long overdue.
-------
APPENDIX A
Synthetic Organid Residues Found in Estuarine Organisms
Taxa
Pesticides
Industrial
Toxicants
Comments
Reference
PISCES
Fish
Fish
Britain
Seatrout
eggs
Fish and
fish oil
Fish in estuary
Fish
Pacific fish
Fish
Pacific.fish-
1i vers
Atlantic fish
Fish
estuarine
DDT, DDE, DDD
DDT, DDE, DDD,
BHC, heptachlor
DDT
DDE, DDD
DDT
DDT
DDT
BHC, heptachlor, aldrin,
toxaphene, chlordane,
methoxychlor, dieldrin,
endrin, DDE, DDD, DDT
DDE, DDT, DDD,
hexachlorobenzene
DDT
PCB's
Aroclor 1254
Aroclor 1242, 12 54,
1260
Shows "biological
magnification"
Residues vary with
species
Woodwell, at al_.,
1967
Moore & Tatton,
1965
Causes spawning failure Butler, 1969
Residue greater in
industrialized coastal
area
Jensen, et al.,
1969
Appears to have no effect Duke, et al.,
on juvenile stage - 1970
(pinfish)
Residues up to 16 ug/g Butler, 1968
Highest concentration in Risebrough,
coastal fish et al., 1967
Mortality following
tidal ditch spray
Croker & Wilson,
1965
Bottom dwellers contain Duke & Wilson,
higher concentration 1971
than pelagic
Higher concentration in Zitko, 1971
surface swimmers
Fatal to predators at Butler, 1966 c
different trophic levels
ro
CO
-------
Taxa
Pesticides
Industrial
Toxicants
Atlantic fish
Phenoclor DP6
Processed and
unprocessed Canadian
fish
Many species
Many species
Groupers; Gulf of
Mexico and Bahamas
Fish
DDE
DDE, DDT
Phthalates
PCB's
Aroclor 1254
Aroclor 1260
HCB
MAMMALIA
Dolphin
Dolphin and Seal
DDT
dieldrin, DDT, DDE,
TDE
Seals
DDE, DDD
PCB
AVES
Bald eagle DDT, DDD
Seabirds; North DDT Aroclor 1254
Atlantic
Comments
Reference
Lower chlorinated PCB's
more frequent in fish
than birds
Low levels were found
in 21 samples of fish
available to the
Canadian consumer
Koeman, et^ al.
1969
Williams, 1973
Compilation of residue
data
Geographic comparisons
Zitko & Choi,
1971
Risebrough &
de Lappe, 1972
Geographic comparisons
Reported 0.002 ppm
(salmon eggs) - 0.11 ppm 1974
(menhaden oil)
Giam, et^ al_.,
1974
Johnson, et al
Concentrated in blubber Butler, 1966 c
Largest amounts in
blubber
Level consistent
throughout all parts of
body
Hoi den &
Marsden, 1967
Jensen, elt al.
1969
Caused death ? Reichel, et al
1969 a
Present in nonmigrating Bourne & Bogan
Arctic birds 1972
-------
Taxa
Pesticides
Industrial
Toxicants
Seabirds and
their predators
Bald eagle and
eggs
Bald eagle and
golden eagle
Terns
DDT
DDE, dieldrin
DDE, DDD, dieldrin,
DCBP, endrin, heptachlor
DDT, DDE
PCB
PCB
Aroclor 1254
Sea birds
(Britain)
Sea birds and
eggs
Brown pelican
eggs
British sea
birds
Sandwich tern
Birds and eggs
Brown pelicans,
petrels and
shearwaters
Cormorant and
gull
DDT, HEOD
DDE, dieldrin
DDT
DDE
telodrin, dieldrin,
endrin, DDE
DDE, DDT
Aroclor 1254
PCB
PCB
Phenoclor DP6
Phenoclor DP6
Aroclor 1254
Aroclor 1254
Gulls eggs
DDE
PCB1 s
Comments
Reference
Data on DDT/PCB ratios
From many areas around
North America
Higher levels in bald
eagles
Deformities in young
Seasonal variation
Highest residues in
freshwater fish-feeding
birds
Eggshells thin
More PCB's than organo-
chlorines
Population decline due
to pesticides
Some parts of mixture
metaboli zed
Geographic comparisons
No dioxins nor benzo-
furans found in eggs
and tissue
Hexachloronaphthalene
present but no dioxins
nor benzofurans found
Risebrough,
et al., 1968 b
Wiemeyer,
et al., 1972
Reichel, et al_.,
1969 b
Hays and
Risebrough, 1972
Robinson,
et al., 1967
Prestt, et al_.,
1970
Schreiber &
Risebrough, 1972
Holmes, et al_.,
1967
Koeman, et al_.,
1967
Koeman, et al_.,
1969
Risebrough &
de Lappe, 1972
Zi tko, et al_.,
1972
Bowes, et al_.,
1973
-------
Taxa
Pesticides
Industrial
Toxicants
Eggs of Florida DDE, dieldrin Aroclor 1254
fish-eating birds
Brain and eggs of DDE
endangered petrel
Bald eagles Aroclor 1254
,J!any species of
fish-eating birds
Shorebirds and fish-
sating birds
DDE
DDE
PCB's
PCB's
Heron egg, Britain
PCB
British seabird
-ggs
Sea birds
dieldrin, DDE, DDT,
BHC, heptachlor
DDT, DDE, DDD
Pacific seabirds DDT, DDE, DDD
Swedish seabirds
DDE, DDD
PCB
Jipds 3nd eggs,
-ong Island, N.Y.
DDT and its metabolites,
dieldrin
10LLUSCA
lollusks,
Sri tain
dieldrin, DDT, DDE,
DDD, heptachlor, BHC
Comments
Reference
2-20 ppm (OD) DDE; 1-161
ppm PCB
0.23 - 0.38 ppm (OD) in
eggs
Confirmation by mass
spectrometry
Compilation of residue
data
Compilation of residue
data and comparison of
DDE residues to eggshell
thickness
Application of mass
spectrometry
Higher levels in eggs
of larger birds
"Biological magnifica-
tion"
Residue levels higher
in California birds
than northern migrants
"Biological magnifica-
tion"
Residues in eggs of
fish-eating birds
Lincer & Sal kind
(sic), 1973
King & Lincer,
1973
Bagley, «rt al_.,
1970
Zitko & Choi,
1971
Keith & Gruchy,
1972
Richardson,
et al., 1971
Moore & Tatton,
1965
Woodwel 1 , et al.
1967
Ri sebrough,
et al., 1967
Jensen, et^ al_.,
1969
Foehrenbach,
1972
Traces present in all
mollusks tested
Moore & Tatton,
1965
-------
Taxa
Pesticides
Industrial
Toxicants
Oysters
DDT
Mussel s
DDE, DDD
PCB's
Oysters
Aroclor 1254
Oysters
Mussels
Oysters, clams,
mussels, snails
DDT
DDT
DDT, DDE, DDD,
dieldrin
PCB
PLANKTON
Phytoplankton
Zooplankton
DDT, DDD, DDE
DDT, DDE, DDD
CRUSTACEA
Sandcrab
DDT, DDE, DDD
Comments
Reference
Rate of shell growth Butler, 1969
indicator of pollution
level
Lower average concentra- Jensen, et al.,
tion in less industrial- 1969
ized area
Shell growth of juvenile Duke, et al.,
completely inhibited 1970
upon exposure
A good monitoring organ- Butler, 1968
ism
Koeman, et^ al_.,
1969
Amounts varied with Foehrenbach,
proximal land use 1972
Concentrations tripled Cox, 1970
1955-1969
Low residues shown for Woodwell,
low trophic level et_ al_., 1967
ro
Concentrations due not Burnett, 1971
only to agriculture
usage but industrial
waste discharge (DDT
plant)
-------
Taxa
Pesticide
Industrial
Toxicant
Crayfish and
shrimp
Shrimp DDT, DDE, DDD
Shrimp
crabs
Fiddler crabs DDT, DDE, DDD
dieldrin
MISCELLANEOUS
Aquatic insect
larvae
Sea urchin DDT compounds
snail
Water & sediment
Suspended organic
matter; San
Francisco Bay
Crown of thorns
Pacific
Green sea turtle DDE
eggs; South
Atlantic
River water;
New England
Aroclor 1254
Aroclor 1254
Aroclor 1254
Aroclor 1254
Phthalate esters
PCB (similar to 1254)
1242, 1248, 1254
phthalate
Comments
Reference
Concentrate rapidly to
equilibrium
Sensitivity correlated
to substantial reduc-
tion in population
Higher concentration
than oysters
Residue levels in Uca
Sanders &
Chandler, 1972
Woodwel1,
et al., 1967
Duke, et al_.,
1970
Foehrenbach,
1972
Failed to metamorphose
to adult stage
All insecticide in.
gonads of sea urchin
Sanders &
Chandler, 1972
Risebrough,
et al., 1967
A gradient with distance Duke, et al.,
from pollution source 1970
Utilization of mass
spectrometry methods
Simoneit,
et al., 1973
Estimated levels of McCloskey &
0.01 - 0.05 ppm Deubert, 1973
0.24 - 1.81 ppm PCB Thompson,
(lipid basis); ND- eŁ al_., 1974
0.08 ppm DDE
Reported 0.9 - 1.9 ppb Hites, 1973
-------
APPENDIX B
Effects, of Synthetic Organic Compounds on Estuarine Organisms
Treatment
Taxa
Organochlorine Insecticides
Observed Effects Reference
Seven pesticides; .1 to 5 clams
ppb; 5 year monitoring oysters
endrin, aldrin, heptachlor oysters
dieldrin, kepone oysters
DDT, 1 ppb clam
Different species take up pesticides at specific
rates. Sublethal long range effects more significant
than acute toxicity.
Linear relation between concentration and shell growth.
Sharp threshold of toxicity relative to shell growth.
No effects for 3 months. 30% mortality 4th month.
Butler, 1971
Butler, 1965
DDT - toxaphene, parathion oysters
together and separately,
<3.0 ppb
12 pesticides ranging from
lindane, 9.10 ppm to CoRal
0.11 ppm
10% less body weight. Tissue changes, loss of resistance Lowe, et al., 1971b
to parasite.
oyster eggs & 50% of eggs develop normally at given concentrations. Davis & Hidu, 1969
larvae
12 pesticides ranging from clam eggs
lindane & aldrin <10 ppm,
to N3514, <1.0 ppm
same as above
DDT ^>1 ppm
<1 ppm
oyster
Remain closed or show spasmodic shell movements at
higher levels;decrease in shell deposition at lower
levels.
Butler, 1966 a
DDT in oil spray, .2-1.6
lb/A
0.3 to 0.8 lb/A
Repeated applications
isopods
amphi pods
prawns
blue crab
spiders
crabs
insects
marsh crabs
High mortality
High mortality
High mortality
10-100% mortality
High mortality
High mortality
High mortality
Resistant,
Springer, 1961
ro
vo
-------
Treatment
Taxa
Ort, :hl i 1 tii
Observed Effects Reference
red mites
fish
molluscs
snails
turtles
frogs
mammals
Not affected
Some deaths
Not affected
¦Not affected
Not affected
Not affected
Not affected
aldrin 0.2 lb/A
gamma BHC 0.2 lb/A
insects
prawns
crabs
fish
crabs
More affected than by DDT
Less affected than by DDT
Less affected than by DDT
Less affected than by DDT
Most toxic insecticide tested
Springer, 1961
DDT - 2 ppm fed
fish
shrimp
50% mortality. DDT in dead laboratory animals less
than in seemingly healthy ones in field.
Butler, 1966 c
DDT 1-500 ppb
DDT 0.2 lb/A
Strobane 0.3 lb/A
BHC 0.1 lb/A
DDT in oil spray,
.3 to 16 lb/A
dieldrin, .0006 to
.012 ppm
.003 ppm
dieldrin
.012 to .003 ppm
.0015 and .0075 ppm
phytoplankton Photosynthesis reduced
Wurster, 1968
fish
crabs
3 species
crabs
Some mortality among animals that could not avoid
pesticides.
Same as DDT
fiddler crabs Fiddler crabs lost ability to escape predators.
snakes High mortality following symptoms of poisoning.
amphibians
lizards
turtles
sailfin molly Killed by 72 hours. Raised serum glutamic oxalo-
acetic transaminase to 1500 to 1700 units.
Survived to 120 hours. Raised SG0T to 6006-11,954
units.
sailfin molly 100% mortality 1st to 31st week.
More than half survived to week 34; growth and repro-
duction adversely affected.
George, et al_., 1957
Herald, 1949
Lane and Scura, 1970
CO
o
Lane and Livingston,
1970
-------
Treatment
Taxa
Or chl e :ti s
Observed Effects Reference
aldrin & dieldrin
DDT 1.0 ppb/2 wks
0.1 ppb/5 wks
DDT, endrin
0.1 to .00001 ppm
DDT 50 ppm
Mirex, 1-5 particles of
bait in standing sea water
or Mi rex in flowing sea
water 1.0 to 0.1 ppb
DDT 2-5 ug/g
DDT CI ppm
DDT 2-4 ppm on food
DDT in flowing sea water
0.1 ppm
0.05 ppm
DDT in flowing sea
water 10 ppb
DDT :0.05 to 0.17 ppb
0.12 to 0.20 ppb
fiddler crab
trout
crayfish
tissues
fish
minnows
eel intestine
juvenile
shrimp
juvenile
shrimp
juvenile blue
crab
fiddler crabs
fish
shrimp
crab
fish
pi nfi sh
oyster
fish
shrimp
shrimp
shrimp
juvenile
shrimp
shrimp
Selectively inhibited cholinesterase activity in
homogenized tissues. Cholinesterase very sensitive to
small amounts of pesticide.
Maximum concentration reached at 2 weeks.
38,000 x test water conc. Loss of 78-87% in 8 weeks.
Avoided water containing pesticides. Did not dis-
tinguish concentration differences.
Guilbaul t, et^ al
1972
Hansen & Wilson, 1970
Hansen, 1969
Inhibition of water absorption. Inhibition of (Na+ and Janicki & Kinter, 1971
K+) activated Mg 2+ - dependent adenosine triphosphatase.
40 to 100% mortality
Up to 100% mortality delayed until shrimp in Mi rex free
water
Up to 96% mortality, delayed
Accumulated Mi rex in bodies
Accumulated Mirex in bodies. Gill parasites reduced.
35-100% mortality
Lowe, et al., 1971 a
Butler, 1968
Accumulated DDT in bodies
Feeding & shell growth stopped. Erratic shell movements. Butler, 1967
50% mortality in 2-4 weeks.
Nimmo and B1 ackman,
Lowered Na+ and K+ in hepatopancreas, change in Na and 1972
K+ only after day 20.
100% mortality
DDT concentrates in hepatopancreas.
hepatopancreas within 6 weeks.
100% mortality 18 to 28 days.
Flushed from
Nimmo, et al., 1971 b
Nimmo, et al., 1970
-------
Treatment
Taxa
Organochlorine Insecticides
Observed Effects Reference
Mirex .001, .1, 1.0 & 10 crab larvae Larval stages prolonged. Increased mortality. Bookhout, et al.,
ppb 1971
DDT 10 ppm on detritus fiddler crabs 100% lost coordination by day 5. Three-fold accumula- Odum, et_ al_., 1969
tion in claw muscles.
Toxaphene
DDE
DDE, dieldrin
DDT group, dieldrin,
heptachlor, toxaphene
DDE
Dieldrin; .1-50 ppm
fish
shrimp, crabs
duck
duck
duck
duck
Established 96 hour TL50 values; includes data on
synergy and histopathology.
Courtenay & Roberts,
1973
Eggshell thinning complete after 4 days on 40 ppm diet; Peakall, et^ al_., 1973
electron microscopy.
20 ppm DDT or 10 ppm dietary doses resulted in eggshell Davison & Sell, 1974
thinning.
Established effects on eggshell thinning.
Haegele& Tucker, 1974
LC50 values varied with age of ducks (1200-1600 ppm). Friend & Trainer,1974
fiddler crabs Levels correlated with maladaptive behavior and mor-
tality. Latent effects.
Klein & Lincer, 1973
Treatment
Taxa
Organophosphate Insecticides
Observed Effects Reference
Parathion
4 pesticides ranging from
guthion .62 ppm, to TEPP
10.
Malathion
dursban;
10-. 01 ppm
Paraoxon, DDVP
parathion, methyl
parathion
oysters
oyster eggs
clam eggs
minnows
fiddler crabs
trout
crayfish
tissues
Sharp threshold of toxicity relative to shell growth.
50% of eggs develop normally.
Did not avoid Malathion
Did avoid Dursban
Selectively inhibited cholinesterase activity in
homogenized tissues. Choiinesterase sensitive to
small amounts of pesticide.
Butler, 19.65
Davis & Hidu, 1969
Hansen, 1969
Guilbault, et al_.,
1972
CO
ro
-------
jrg, t iosr 3 1
Treatment Taxa Observed Effects Reference
Malathion, naled,
guthion and parathion
fishes and
pink shrimp
Revealed comparative AChE inhibition.
Coppage & Matthews,
1974
Parathion
duck
Established effect on eggshell thinning.
Haegele & Tucker,1974
Treatment
Taxa
Carbamate Insecticides
Observed Effects
Reference
Sevin 0.1 ppm
juvenile fish
Survived normally, neural parasite may not be related
to toxicant.
Lowe, 1967
Sevin 0.01-10 ppm
minnows
Did not avoid Sevin
Hansen, 1969
Sevin
gastropod
(oyster drill)
Swelling at 6-7 hours exposure.
Wood & Roberts, 1963
Matacil, mesurol,
zectran, baygon, sevin
fiddler crabs
crayfish
trout
Selectively inhibited cholinesterase activity in
homogenized tissues. Choiinesterase very sensitive
to small amounts of pesticides.
Guilbault, et al.,
1972
Treatment
Taxa
Herbicides, Bactericides, etc.
Observed Effects Reference
12 herbicides ranging
from amitrol 733.70 ppm
to si 1 vex 2.4 ppm
nemagon, sevin;
oyster eggs
clam eggs
50% developed normally
Davis & Hidu, 1969
19 bactericides, algi-
cides, fungicides from
untinted sulmet 1000
ppm to phygon .014 ppm
oyster eggs
clam eggs
50% developed normally
GJ
CO
2,4-D acid
duck
Established effect on eggshell thinning.
Haegele & Tucker, 1974
-------
Treatment
Taxa
'bi s, er les.
Observed Effects ¦ Reference
4 herbicides In sea
water
Nitrilotriacetic acid
2,4-D, 0.01 - 10 ppm
antimycin A 7 ppb
Polystream (chlorinated
benzenes)
6 genera algae
phytoplankton
minnows
Carbohydrate concentration depressed. Varies with
salinity.
Low toxicity as long as chelate : metal ratio favor-
able; NTA alone, trace metal deficiency.
Avoidance of herbicide
38 species fish Killed in three days
other fish
oysters
plankton
crabs
oyster drill
No effect
Under recommended dosage, 50% of animals killed by
day 7.
Walsh & Grow, 1971
Erikson, et^ al_.,
1970
Hansen, 1969
Finucane, 1969
Wood & Roberts,
1963
Treatment
Taxa
Industrial Toxicants
Observed Effects Reference
Aroclor 1254
.94 - 100 ppb
Aroclor 1254
2.5 - 3.5 ppb
Aroclor 1254 in
Corexit 7664
colloidal solution
emulsions
Aroclor 1254
1 ppb to 56 days
5 ppb 14-45 days
Aroclor 1254
100 ppb 48 hours
juvenile shrimp 51 to 100% mortality
adult shrimp 50% mortality, accumulated in tiepatopancreas
23% died after return to sea water
Gammarus
Gammarus
fish
shrimp
oysters
pinfish
Lethal threshold 0.001 to 0.01 ppm
Lethal threshold .01 to .1 ppm
No apparent effect at 1 ppb;
Mortality occurred, though delayed at 5 ppb.
100% mortality
shell growth inhibited
concentrated PCB
Nimmo, et al., 1971b
Wildish, 1970
Hansen, et al., 1971
Duke, et. al_. , 1970
CO
-------
Treatment
Taxa
us
Observed Effects
7 ant
Reference
5 ppb 20 days
Aroclor 1242 and
Aroclor 1254 +
radiocarbon
Aroclor 1242 in
water .01 to .1 ppm
Aroclor 1254 in
sediment 61.0 ppm
(dry wt.) to 1.4 ppm
for 30 days
Aroclor 1221; 7.5 -
75 ppm
Aroclor 1254
Aroclor 1254;
0.001 - 10 ppm
Aroclor 1016
Aroclor 1254
Aroclor 1254
Aroclors 1232, 1242,
1248, 1254, 1260, 1262
Aroclor 1254
Dioxin (TCDD) in
water and food
Dibenzoftirans
shrimp
crabs
shrimp
crabs
killifish
shrimp
shrimp
fishes
oyster
shrimp
fish
oyster
duck
duck
duck
salmonids
salmonids
72% mortality after day 10
concentrated PCB
phytoplankton Radiocarbon uptake reduced at as low as 1-2 ppb.
Moore & Harriss,
1972
marine diatom Inhibited growth, RNA synthesis and chlorophyl index. Kiel, eŁ al_., 1971
Amount of PCB residue in animal varies with amount in Nimmo, |